Optical-Optical Double Resonance Spectroscopy of the 1g(P1)-AΠ (1u)-XΣg Transition of I2

Optical-optical double resonance spectroscopy was used to study the 1_g(³P₁) ion-pair state of I₂ correlating to I⁻(¹S)+I⁺³P₁) at the dissociation limit. We gained access to the 1_g(³P₁) state though the A³Π (1_u) state in the (1+1) photon-excitation scheme. The pump laser excited the A³Π (1_u)-X¹Σ_g⁺ transition at a fixed frequency for state selection. The probe laser was scanned to detect the 1_g(³P₁)-A³Π (1_u) resonance by monitoring the ultraviolet emission from the 1_g(³P₁) state at 278 nm. The 1_g(³P₁) state was observed in a vibrational progression consisting of P and R doublets. An energy level analysis was carried out for the 1_g(³P₁) state in the 0≤ v ≤ 14 and 12≤J≤135 range, which led to a set of molecular parameters including the Ω-doubling constant. The Ω-doubling of the 1_g(³P₁) state was discussed by the pure precession model and interpreted to occur through the heterogeneous coupling with the 0_g⁻(³P₁) state correlating to the same ionic asymptote.     

Singlet-triplet anticrossings between ungerade states of H2

Singlet-triplet anticrossings in the H₂ molecule have been observed between two ungerade states, B′(3p)¹Σ_u⁺ and f(4p)³Σ_u⁺. This is the first time that an observed H₂ anticrossing has involved a state which can radiate directly to the ground state. Analysis yields accurate values for the zero field separations between two pairs of rotational and vibrational levels. It also yields a value for the Fermi contact interaction in the triplet state as well as the difference in the orbital angular momentum g factors for the two states. From linewidth measurements, we deduce a rigorous lower limit to the radiative lifetime of the B′¹Σ_u⁺ state and a (nearly equal) most reasonable value for it. It is shown that the perturbation between the two states is quite weak leading to little singlet-triplet mixing in zero field. The experimental data establish that the oscillator strength for the forbidden transition from the ground state to the f(4p)³Σ_u⁺ state is at least seven orders of magnitude smaller than that of the allowed transition to the B′¹Σ_u⁺ state.     

Stimulated Emission Pumping Spectroscopy of SiH2: First Observation of the Spin-Orbit Interaction between the X?A1 and the ãB1 States

Stimulated emission pumping spectra of the ùB₁-X?¹A₁ transition of the SiH₂ radical were observed in order to obtain information about the ã³B₁ state through the spin-orbit interaction. The vibrational level structure of the X? state, which is the basis for the present observation of the triplet state, was well described with a polyad structure, in which both the 1ν₁ : 2ν₂ Fermi and the 2ν₁ : 2ν₃ Darling-Dennison anharmonic resonances were considered. In the P=10 polyad, four sets of spin-orbit perturbations were observed for the first time. The triplet state observed at about 9640 cm⁻¹ from the (000) level of the X? state was tentatively assigned as the ã³B₁ (030) level. An analysis of the spin-orbit interaction showed that the interaction energies of the spin-orbit coupling are 0.73-3.13 cm⁻¹. This value is rather smaller than that expected based on the comparison with CH₂. This is considered to be due to poor overlap between the vibrational wave functions in the ã and the X? state.     

Experimental study of the Na2 3Πg state

The 3¹Π_g state of Na₂ is experimentally investigated by using high resolution cw optical-optical double resonance spectroscopy. A single line Ar⁺ laser (total of 9 lines) is used to pump the sodium dimers from thermally populated ground state to the intermediate B¹Π_u state. Then a single mode Ti:sapphire laser is used to probe the 3¹Π_g state. Violet fluorescence from highly Rydberg excited states (mainly 2³Π_g or 3³Π_g states which are transferred from 3¹Π_g state via collisions) to the state is monitored by a filtered photomultiplier tube and a lock-in amplifier. Compared with previous studies [C.C. Tsai, J.T. Bahns, W.C. Stwalley, J. Chem. Phys. 99 (1993) 7417], a wider range of rotational quantum numbers of data field are observed. A set of Dunham coefficients and the Rydberg-Klein-Rees potential energy curve of the 3¹Π_g state are deduced from all the observed rovibrational levels.     

Ligand-to-metal charge-transfer quenching of the Eu(D1) state in europium-doped tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium (III)

Rate constants for the decay of the Eu³⁺(⁵D₁) state in dilute Eu³⁺-doped tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium(III) are reported for a temperature range 50-315 K. A temperature-independent contribution of 1.3×10⁶ s⁻¹ is attributed to carbonyl mediated ⁵D₁→⁵D₀ relaxation. A temperature-dependent contribution, that has been parameterized as k_CT=Ae^−E_a/kT with E_a=2540±140 cm⁻¹ and A=1.3×10¹² s⁻¹ is attributed to quenching of ⁵D₁ by a low-lying ligand-to-metal charge-transfer state (CTS). The height of the activation barrier, E_a, relative to the previously reported height for charge-transfer quenching of the Eu³⁺(⁵D₀) state in the pure europium analog (J. Phys. Chem. 100 (1996) 9216) is discussed in terms of mechanistic implications. Specifically, these data strongly suggest that quenching of ⁵D₁ by the charge-transfer state is mediated by the ⁵D₀ state with a novel, indirect mechanism.     

Spin-selective electron tunneling from excited FA centers to F+ centers in CaO

From pulsed phosphorescence microwave double resonance experiments it is established that electron tunneling between F_A and F⁺ centers in CaO occurs from F_A centers in the excited ³A₁ state. Only the radiative sub-levels within this ³A₁ state act as precursor states in the electron transfer process. The tunneling rate at 1.2 K is determined to be 1.5±0.2s^-1.     

Lowest excited states of 2-aminopurine

Absorption and fluorescene spectra and quantum yields of emission over a wide range of pH and solvent polarity were measured for 2-aminopurine and 2-dimethylaminopurine. An increase in dipole moment and a rise of pK values for N₁(N₃) ring atom protonation in the excited state were demonstrated. Thus, the lowest excited singlet state shows partially the (1, a_π¹) configuration. The polarization, lifetimes and the phosphorescence-to-fluorescence ratios indicate that spin-orbit coupling of ¹(n, π¹) and ¹(1, a_π¹) with the lowest triplet state is the main source of phosphorescence intensity. The matrix element of spin-orbit coupling of ¹(n, π¹) to the T₁ state is about 33 times larger than that of ¹(1, a_π¹). The temperature- dependent process of 2-aminopurine fluorescence quenching in either is presumably due to the thermal population of the second excited triplets state of (n, π¹) configuration, which can approximately be located at 370 cm^-1 above the lowest (1, a_π¹) singlet.     

Gas phase high temperature photoelectron spectroscopy: an investigation of the transition metals scandium and vanadium

The He(I) photoelectron spectra of atomic scandium and vanadium have been recorded in the gas-phase. For scandium two bands associated with a (4s)^?1 ionization and one band associated with a (3d)^?1 ionization of the neutral atom have been observed. Measurement of their relative intensities allows the σ_3d:σ_4s photoionization cross-section ratio in atomic scandium to be estimated as 57.1 ± 9.0. In the atomic vanadium spectrum, six bands were seen. Four of these correspond to (3d)^?1 and (4s)^?1 ionizations of the ground state of the neutral atom, the V a⁴F state, whereas two bands correspond to (3d)^?1 ionizations of an excited state, the V a₆D state, which is approximately 2100 cm^?1 above the ground state. Measurement of the intensities of bands arising from the V a₄F state allows σ_3d:σ_4s to be estimated as 29.8 ± 2.5 for vanadium. Spectra of vanadium have been recorded with both single- and multi-detector photoelectron spectrometers. Comparison of the data acquisition rates obtained with both spectrometers demonstrates the advantage of using a multidetector instrument in high temperature photoelectron spectroscopy.     

The Reid93 Potential Triton in the Unitary Pole Approximation

The Reid93 potential provides a representation of the nucleon–nucleon (NN) scattering data that rivals that of a partial wave analysis. We present here a unitary pole approximation (UPA) for this contemporary NN potential that provides a rank one separable potential for which the wave function of the deuteron (³S₁-³D₁) and singlet anti-bound (¹S₀) state are exactly those of the original potential. Our motivation is to use this UPA potential to investigate the sensitivity of the electric dipole moment for the deuteron and ³H and ³He to the ground state nuclear wave function. We compare the Reid93 results with those for the original Reid (Reid68) potential to illustrate the accuracy of the bound state properties.     

Ab initio calculations of neutral and charged impurity centers of manganese and chromium in strontium titanate

This paper presents the results of ab initio calculations of the equilibrium geometry, the electronic structure, and the spin and charge densities for neutral and negatively charged defects produced by the Mn and Cr impurities in the B position of the SrTiO₃ structure. It has been shown that, in both cases, the neutral defect is an acceptor center, while the singly charged defect is a donor center. It has been found that doubly charged defects are polar, have the symmetry C _4v, and reside in the ionic configurations ⁵Mn³⁺ + ³Ti³⁺ and ⁴Cr³⁺ + ³Ti³⁺, respectively. In each case, there is a pair of almost energy-degenerate electronic states (⁴ B ₁ and ⁶ B ₁ for Mn and ³ A ₁ and ⁵ A ₁ for Cr), which differ only in the direction of the spin of the electron polaron localized at one of the neighboring titanium atoms. For the manganese impurity, the energy of the polar state ⁶ B ₁ is only 0.174 eV lower than that of the state ⁶ A _1g (O _h ) with the Mn²⁺ ion in the high-spin state. A new mechanism of dielectric relaxation in STO: Mn has been proposed.     

Low-lying intrinsic energy levels in the nucleus170Ho

The band-head energies of the two-quasiparticle states expected in the doubly odd deformed nucleus¹⁷⁰Ho are calculated for a zero range residual interaction. The results are compared with the available experimental information. It is concluded that the ground state has the Nilsson configuration 6⁺{7/2^?[523↑] _p }+5/2[512↑] _n being the 2.76m isomer whereas the 43s isomer is the 1⁺ ∑=0 state arising from the same configuration and lies at about 100 keV excitation energy in agreement with the experiment. The first excited state in this nucleus is predicted to be the 4^?{3/2⁺[411↑] _p +5/2^?[521↑] _n } state close to the ground state with the corresponding 1^? ∑=0 member expected to appear well above the 1⁺ isomer.     

A predissociative triplet Rydberg state of the nitrogen molecule studied by near-infrared diode laser kinetic spectroscopy

A new ³Π-³Σ band was observed in a discharge plasma of the nitrogen molecule and helium using near-infrared diode laser kinetic spectroscopy. All the lines in this band exhibited line broadening of more than 0.1 cm⁻¹. Rotational analysis revealed that the lower state of the transition was the state of N₂, which had already been studied in the D³Σ-E³Σ band. The term value and rotational constant suggested that the upper state is the G³Π_u Rydberg state with an electron configuration of (N₂⁺:X²Σ core)(3pπ_u). The line broadening is attributed to predissociation through a homogeneous interaction with a repulsive Π_u state.     

Photoionization of molecular oxygen in the X3Σg− and a1Δg states

Calculations are carried out, at similar levels of approximation, of the photoionization cross-sections for the ground X³Σ_g^? and metastable a¹Δ_g states of O₂ leading to the X²Π_g state of O₂⁺. Estimates, based upon measurements for the X³Σ_g^? state, are made of the photoionization cross-section of the a¹Δ_g state for transitions populating excited states of O₂⁺.     

Rotational analysis of the c3Πu–b3Πg system of P2

The rotationally resolved spectra of the c³Π_u–b³Π_g system of P₂ in the 16620–17860 cm^?1 region is reanalyzed here to obtain more assignments of the rotational lines and more accurate molecular constants. Approximately 500 spectral lines were assigned to six subbands: the Ω=0, 1 and 2 components of the (2, 3) band, the Ω=0 and 2 components of the (1, 3) band and the Ω=2 component of the (1, 2) band. Because of perturbations in the c³Π_u (υ=2) state, the Λ-doubling in the ³Π₂–³Π₂ subband of the (2, 3) band was resolved. By the weighted nonlinear least-squares fitting using two types of effective Hamiltonians, more accurate molecular constants for the υ′=1 and 2 levels in the c³Π_u state and for the υ″=2 and 3 levels in the b³Π_g state of P₂ were derived.     

EPR study of Ce ions in lutetium silicate scintillators Lu2Si2O7 and Lu2SiO5

Two Ce³⁺-doped scintillator crystals, LSO (Lu₂SiO₅:Ce) and LPS (Lu₂Si₂O₇:Ce), are studied by EPR spectroscopy. The analysis indicates that Ce³⁺ substitutes for Lu³⁺ ion in a C₂-symmetry site for LPS and in two C₁-symmetry sites for LSO, with a preference for the largest one, with 6+1 oxygen neighbors. Angular dependence of the EPR spectrum shows that the electronic ground state of Ce³⁺ is different in these two matrices. It is mainly composed of |M_J|=5/2 state in LPS and |M_J|=3/2 state in LSO. The temperature dependence of the linewidth shows a noticeably long spin lattice relaxation time, especially in LPS, which is the result of a stronger crystal field in LPS than in LSO.     

Li- and V-NMR study of LiVS2

⁷Li- and ⁵¹V-NMR have been measured to make clear the electronic state in a two-dimensional triangular lattice LiVS₂. Knight shift of both ⁷Li- and ⁵¹V-NMR is almost independent of temperature below the phase transition temperature T_c of about 310 K from the paramagnetic state to non-magnetic state. The ⁵¹V- spin-lattice relaxation rate 1/T₁ reveals an exponential temperature dependence below T_c, indicating a gap structure of electronic state. These results are consistent with a non-magnetic state with a trimer singlet of V³⁺ spins below T_c.     

The production and loss ofN 2 + ions in the nitrogen afterglow

The time dependence of the number density of nitrogen ions was studied in the pressure range of about 0.1 to 1.7 Torr by means of mass spectrometric probing of decaying nitrogen plasmas. The analysis of theN ₂ ⁺ decay curves showed thatN ₂ ⁺ ions are produced in the afterglow by collisions between metastable nitrogen molecules. Energy level and radiative lifetime considerations indicate that one of the metastable molecules is in thea′ ¹∑ _u ^} state, while the other metastable molecule may be in the same state or in theA ³∑ _u ⁺ or³ Δ _u state. The surface catalytic efficiency for de-excitation of the metastable molecules involved upon striking the molybdenum covered plasma container walls was estimated to be smaller than 2×10^?3 at a pressure of 0.09 Torr. If both interacting metastable molecules are in the a′¹ bE _u ^} state the measurements result in a value of 1.3×10^?18 cm² for the cross section for destruction of this state by collisions with ground state nitrogen molecules.     

Absolute Position of the D′2g(P2) Ion-Pair State of I2 Determined by Perturbation-Facilitated Optical-Optical Double Resonance

We have reexamined the sequential two-photon absorption of I₂ from the X¹Σ_g⁺ ground state to the lowest D′2_g(³P₂) ion-pair state using the high vibrational level of the B³Π(0_u⁺) state as an intermediate. The double resonance transition to the D′2_g(³P₂) state was found to occur through the B³Π(0_u⁺)-b′2_u coupled state by hyperfine interaction, which permits to mix the different J levels of different electronic states. We elucidated the B³Π(0_u⁺)-b′2_u coupling schemes in the intermediate states. The double resonance spectra recorded for the D′2_g(³P₂) state in the range v=0-30 were used to determine the absolute energy of the D′2_g(³P₂) state. The molecular parameters of the D′2_g(³P₂) state obtained in this study are Y₀₀=40 388.783(2), Y₁₀=103.956 46(57), Y₂₀=−0.207 717(51), Y₃₀=2.199(13)×10⁻⁴, Y₀₁=0.020 528 18(62), and Y₁₁=−5.1753(48)×10⁻⁵ (all in cm⁻¹ and σ in parentheses). An RKR potential curve constructed using these constants is reported. Combined with the data on the D′2_g(³P₂)-A′³Π(2_u) transition from Zheng et al. (J. Chem. Phys.96, 4877 (1992)), we can locate the A′³Π(2_u) v=0 state at 10 096.444(6) cm⁻¹ above the ground state.     

The pure rotational spectrum of ZnO in the XΣ and aΠi states

The pure rotational spectrum of ZnO has been measured in its ground X¹Σ⁺ and excited a³Π_i states using direct-absorption methods in the frequency range 239-514 GHz. This molecule was synthesized by reacting zinc vapor, generated in a Broida-type oven, with N₂O under DC discharge conditions. In the X¹Σ⁺ state, five to eight rotational transitions were recorded for each of the five isotopologues of this species (⁶⁴ZnO, ⁶⁶ZnO, ⁶⁷ZnO, ⁶⁸ZnO, and ⁷⁰ZnO) in the ground and several vibrational states (v = 1-4). Transitions for three isotopologues (⁶⁴ZnO, ⁶⁶ZnO, and ⁶⁸ZnO) were measured in the a³Π_i state for the v = 0 level, as well as from the v = 1 state of the main isotopologue. All three spin-orbit components were observed in the a³Π_i state, each exhibiting splittings due to lambda-doubling. Rotational constants were determined for the X¹Σ⁺ state of zinc oxide. The a³Π_i state data were fit with a Hund’s case (a) Hamiltonian, and rotational, spin-orbit, spin-spin, and lambda-doubling constants were established. Equilibrium parameters were also determined for both states. The equilibrium bond length determined for ZnO in the X¹Σ⁺ state is 1.7047 Å, and it increases to 1.8436 Å for the a excited state, consistent with a change from a π⁴ to a π³σ¹ configuration. The estimated vibrational constants of ω_e ∼ 738 and 562 cm⁻¹ for the ground and a state agreed well with prior theoretical and experimental investigations; however, the estimated dissociation energy of 2.02 eV for the a³Π_i state is significantly higher than previous predictions. The lambda-doubling constants suggest a low-lying ³Σ state.